WO2012132921A1 - 太陽電池用保護シートおよびその製造方法、ならびに太陽電池モジュール - Google Patents

太陽電池用保護シートおよびその製造方法、ならびに太陽電池モジュール Download PDF

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Publication number
WO2012132921A1
WO2012132921A1 PCT/JP2012/056669 JP2012056669W WO2012132921A1 WO 2012132921 A1 WO2012132921 A1 WO 2012132921A1 JP 2012056669 W JP2012056669 W JP 2012056669W WO 2012132921 A1 WO2012132921 A1 WO 2012132921A1
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Prior art keywords
layer
solar cell
protective sheet
thermoplastic resin
resin layer
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PCT/JP2012/056669
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English (en)
French (fr)
Japanese (ja)
Inventor
誉也 ▲高▼梨
内藤　真人
田矢　直紀
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リンテック株式会社
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Priority to EP12763956.5A priority Critical patent/EP2693490A4/en
Priority to US14/007,665 priority patent/US20140069495A1/en
Priority to CN2012800161036A priority patent/CN103460400A/zh
Publication of WO2012132921A1 publication Critical patent/WO2012132921A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a solar cell protective sheet used as a surface protective sheet or a back surface protective sheet of a solar cell module, a method for producing the same, and a solar cell module using the solar cell protective sheet.
  • Solar cell modules that convert solar light energy into electrical energy are attracting attention as a clean energy source that can generate electricity without discharging carbon dioxide in response to environmental problems such as air pollution and global warming.
  • a solar cell module is composed of a solar cell made of crystalline silicon, amorphous silicon, or the like that performs photoelectric conversion, a sealing material (filling layer) made of an electrical insulator that seals the solar cell, and the surface of the sealing material. It is comprised from the surface protection sheet (front sheet) laminated
  • the solar cells and sealing material are protected from wind, rain, moisture, dust, mechanical shock, etc. It is necessary to keep the inside of the battery module sealed from the outside air. For this reason, the protection sheet for solar cells is required to have moisture resistance and weather resistance that can withstand long-term use.
  • Patent Document 1 discloses a solar cell module in which a silicon power generation element is sealed with a sealing material made of an ethylene-vinyl acetate copolymer sheet, and a back sheet is laminated on the back surface of the sealing material.
  • a back sheet a sheet in which a fluorine-based plastic film having weather resistance (Tedlar film manufactured by DuPont) is bonded to one side or both sides of a layer that prevents water vapor permeation, such as metal, is disclosed. This back sheet is heat-bonded to the sealing material.
  • the conventional back sheet as in Patent Document 1 has a problem that the back sheet peels off from the sealing material and water vapor enters the sealing material because of low adhesion to the sealing material.
  • Patent Document 2 discloses a back sheet laminated on the back surface of a filler in a solar cell module using an ethylene-vinyl acetate copolymer as a filler, and includes an epoxy compound and / or a silane compound.
  • a heat-fusible layer made of a heat-fusible resin composed mainly of a graft-modified ethylene- (meth) acrylate copolymer, ethylene-vinyl acetate copolymer, or a mixture thereof is laminated on a heat-resistant film.
  • Patent Document 2 when manufacturing a back sheet, a heat-fusible layer is laminated on a heat-resistant film by an extrusion coating method.
  • Such a method of forming a heat-fusible layer has high productivity, but has a problem that shrinkage occurs due to cooling of the heat-fusible layer and curls occur in the width direction or the flow direction of the roll. If the solar cell module is warped along with the curl of the back sheet, not only will the malfunction occur when the solar cell module is installed, but the solar cell module may be damaged.
  • This invention is made
  • the present invention provides a solar cell protective sheet comprising a base material and a thermoplastic resin layer laminated on at least one surface of the base material,
  • the plastic resin layer contains at least one pigment selected from the group consisting of titanium oxide, talc, magnesium oxide, cerium oxide, barium sulfate, calcium carbonate, and carbon black.
  • the solar cell protective sheet according to the above invention (Invention 1) has excellent adhesion to the sealing material of the solar cell module, and can suppress warping that occurs in the solar cell module because the curl amount is small.
  • thermoplastic resin layer is a single layer, has a density of 875 to 920 kg / m 3 , and has a heat of fusion ⁇ H obtained by a differential scanning calorimeter of 100 J / g or less.
  • Resin may be the main component (Invention 2).
  • the pigment is preferably contained in the thermoplastic resin layer in an amount of 2.5 to 35% by mass (Invention 3).
  • the said thermoplastic resin layer is laminated
  • the olefin resin of the second layer has a density of 875 to 920 kg / m 3 and a heat of fusion ⁇ H obtained by a differential scanning calorimeter of 100 J / g. The following is preferable (Invention 4).
  • the pigment is preferably contained in the second layer (Invention 5).
  • the pigment is preferably contained in the second layer in an amount of 2.5 to 35% by mass (Invention 6).
  • the olefin resin preferably contains 60 to 100% by mass of ethylene as a monomer unit (Invention 7).
  • the first layer mainly comprises a copolymer of ethylene and at least one selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester and vinyl acetate. It is preferable to use as a component (Invention 8).
  • the total content of (meth) acrylic acid, (meth) acrylic acid ester and vinyl acetate as monomer units in the copolymer of the first layer is 2 to 40. It is preferable that it is mass% (Invention 9).
  • (meth) acrylic acid ester as a monomer unit in the copolymer of the first layer is methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and It is preferably at least one selected from the group consisting of methyl acrylate (Invention 10).
  • thermoplastic resin layer is preferably formed by extrusion coating (Invention 11).
  • thermoplastic resin layer is preferably a layer bonded to a sealing material constituting the solar cell module (Invention 12).
  • the present invention is a method for producing a protective sheet for a solar cell comprising a substrate and a thermoplastic resin layer laminated on at least one surface of the substrate, and the density is 875 to 920 kg / m.
  • the main component is an olefin resin having a heat of fusion ⁇ H obtained by a differential scanning calorimeter of 100 J / g or less, and consists of titanium oxide, talc, magnesium oxide, cerium oxide, barium sulfate, calcium carbonate, and carbon black.
  • a protection for solar cells wherein the thermoplastic resin layer is formed by extrusion-coating a thermoplastic resin composition containing at least one pigment selected from the group on at least one surface of the substrate.
  • a method for producing a sheet is provided (Invention 13).
  • the present invention is a method for producing a protective sheet for a solar cell, comprising a base material and a thermoplastic resin layer laminated on at least one surface of the base material, the adhesive sheet being bonded to the base material
  • a first resin composition exhibiting properties, an olefin resin having a density of 875 to 920 kg / m 3 , a heat of fusion ⁇ H obtained by a differential scanning calorimeter of 100 J / g or less, and a titanium oxide
  • this invention is a solar cell module provided with the photovoltaic cell, the sealing material which seals the said photovoltaic cell, and the protective sheet laminated
  • the solar cell module is characterized by comprising a protective sheet for a solar cell (invention 12), and the protective sheet is bonded to the sealing material via the thermoplastic resin layer (invention 15). ).
  • the protective sheet for solar cell according to the present invention is excellent in adhesion to the sealing material of the solar cell module, and can suppress warpage occurring in the solar cell module because the curl amount is small. Moreover, according to the manufacturing method of the protection sheet for solar cells which concerns on this invention, the protection sheet for solar cells which has the above outstanding effects is obtained. Furthermore, in the solar cell module according to the present invention, the adhesiveness between the sealing material and the protective sheet is excellent, and warpage due to curling of the protective sheet is suppressed.
  • the solar cell protective sheet 1 ⁇ / b> A includes a base material 11 and a thermoplastic resin layer 12 ⁇ / b> A laminated on one surface (upper surface in FIG. 1) of the base material 11. And.
  • This solar cell protective sheet 1A is preferably used as a back surface protective sheet (back sheet) of a solar cell module.
  • the base material 11 As the base material 11, it is generally sufficient that the base material 11 has electrical insulation and the thermoplastic resin layer 12 ⁇ / b> A can be laminated, and a material mainly composed of a resin film is usually used.
  • a resin film generally used as a resin film in a solar cell module back sheet is selected.
  • resin films include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyamide resins such as nylon (trade name), polycarbonate resins, and polystyrene.
  • PET polyethylene terephthalate
  • a film or sheet made of a resin such as a resin, a polyacrylonitrile resin, a polyvinyl chloride resin, a polyvinyl acetal resin, a polyphenylene sulfide resin, a polyphenylene ether resin, or a fluorine resin is used.
  • a film made of a polyester resin is preferable, and a PET film is particularly preferable.
  • the said resin film may contain various additives, such as a pigment, a ultraviolet absorber, a ultraviolet stabilizer, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and an antiblocking agent, as needed.
  • a pigment examples include titanium dioxide and carbon black.
  • the ultraviolet absorber examples include benzophenone series, benzotriazole series, oxalic acid anilide series, cyanoacrylate series, and triazine series.
  • the surface of the resin film on which the thermoplastic resin layer 12A is laminated is preferably subjected to surface treatment such as corona treatment, plasma treatment, and primer treatment in order to improve adhesion to the thermoplastic resin layer 12A. .
  • the thickness of the base material 11 is appropriately set based on electrical insulation properties, water vapor barrier properties, etc. required for the solar cell module.
  • the thickness is preferably 10 to 300 ⁇ m. More specifically, when the substrate 11 is a PET film, the thickness is preferably 10 to 300 ⁇ m, more preferably 20 to 250 ⁇ m, from the viewpoint of electrical insulation and weight reduction. It is particularly preferable that the thickness is ⁇ 200 ⁇ m.
  • the thermoplastic resin layer 12A in the present embodiment is for bonding the solar cell protective sheet 1A to the sealing material of the solar cell module, but the present invention is not limited to this.
  • the thermoplastic resin layer 12 ⁇ / b> A in the present embodiment is a single layer, contains a thermoplastic resin as a main component, and contains a pigment.
  • Examples of the pigment include titanium oxide, talc, magnesium oxide, cerium oxide, barium sulfate, calcium carbonate, and carbon black. One type can be used alone, or two or more types can be used in combination. .
  • thermoplastic resin layer 12A contains the above-mentioned pigment
  • the pigment enters the crystal structure when the thermoplastic resin crystallizes.
  • the thermoplastic resin is restrained by the pigment, the thermoplastic resin layer 12A is less likely to shrink when cooled from the heat-melted state, and the curl amount of the solar cell protective sheet 1A becomes small. Thereby, it can suppress that curvature arises in a solar cell module resulting from the curl of the protection sheet 1A for solar cells.
  • the warpage of the solar cell module is suppressed when the curl amount in the vertical direction is 20 mm or less.
  • the solar cell protective sheet 1A provided with the thermoplastic resin layer 12A containing the pigment the curl amount can be suppressed to 20 mm or less.
  • titanium oxide is preferable as the white pigment and carbon black is preferable as the black pigment in terms of color developability, availability, and cost.
  • the particle diameter of the pigment is not particularly limited, but the average particle diameter is preferably 0.005 to 10 ⁇ m, and particularly preferably 0.01 to 5 ⁇ m.
  • the pigment is preferably contained in the thermoplastic resin layer 12A in an amount of 2.5 to 35% by mass, particularly preferably 2.5 to 32.5% by mass, and more preferably 3.0 to 30% by mass. It is preferable.
  • the titanium oxide is preferably contained in the thermoplastic resin layer 12A in an amount of 3.0 to 30% by mass, particularly preferably 5.0 to 25% by mass, It is preferably contained in an amount of 7.5 to 20% by mass.
  • carbon black is used as the pigment, the carbon black is preferably contained in the thermoplastic resin layer 12A in an amount of 2.5 to 30% by mass, particularly preferably 2.75 to 25% by mass, Is preferably contained in an amount of 3.0 to 20% by mass.
  • the curl amount of the solar cell protective sheet 1A can be kept small, and the thermoplastic resin layer 12A can be sufficiently made to have a desired color or reflectance. it can. Moreover, the adhesiveness of 12 A of thermoplastic resin layers with respect to the sealing material of a solar cell module can be maintained because content of a pigment is below said upper limit.
  • the thermoplastic resin layer 12A in the present embodiment is mainly composed of a thermoplastic resin. However, since the thermoplastic resin has a heat sealing action, the thermoplastic resin layer 12A has adhesiveness to the sealing material of the solar cell module. It will be expensive.
  • Thermoplastic resin as a main component of the thermoplastic resin layer 12A has a density of 875 ⁇ 920kg / m 3, in particular 880 ⁇ 915kg / m 3, the heat of fusion ⁇ H obtained by differential scanning calorimeter 100 J / g or less, Particularly preferred is an olefin resin of 95 J / g or less.
  • the density is a value obtained by measurement according to JIS K7112: 1999.
  • the lower limit of the heat of fusion ⁇ H is naturally determined by the relationship with the density and the skeleton of each resin, but is theoretically preferably 0.
  • an olefin resin having a low density or an ultra-low density and a small heat of fusion ⁇ H, that is, low crystallinity has a small shrinkage rate even when cooled from a heated and melted state. Therefore, by using the olefin-based resin as a main component of the thermoplastic resin layer 12A, even when the thermoplastic resin layer 12A is formed on the base material 11 by extrusion coating, stress acting toward the base material 11 is hardly generated. Therefore, the curl amount of the solar cell protective sheet 1A is smaller. Thereby, it can suppress more effectively that curvature arises in a solar cell module resulting from the curl of the protection sheet 1A for solar cells.
  • the density of the olefin-based resin is less than 875 kg / m 3 , tackiness occurs in the thermoplastic resin layer 12A, blocking occurs in the wound solar cell protective sheet 1A, and the solar cell protective sheet 1A. There is a possibility that a blocking mark may be attached to the protective film 1 or the wound solar cell protective sheet 1A cannot be unwound.
  • the density of the olefin resin exceeds 920 kg / m 3 or the heat of fusion ⁇ H of the olefin resin exceeds 100 J / g, the curl amount of the solar cell protective sheet 1A tends to increase (however, Curling can be suppressed by blending the above pigments).
  • the melt flow rate (MFR) of the olefin resin is preferably 1 to 20 g / 10 min, and particularly preferably 2 to 10 g / 10 min.
  • MFR melt flow rate
  • the thermoplastic resin layer 12A can be formed by extrusion coating.
  • olefin resin for example, low density polyethylene (LDPE, density: 910 kg / m 3 or more and less than 930 kg / m 3), very low density polyethylene (VLDPE, density: 880 kg / m 3 or more and less than 910 kg / m 3)
  • polyethylene resin polypropylene resin (PP), polyethylene-polypropylene polymer, olefin elastomer (TPO), cycloolefin resin, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate-maleic anhydride copolymer
  • Ethylene- (meth) acrylic acid copolymer ethylene-acrylic acid ester copolymer, ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, etc., one kind alone or two or more kinds Can be used in combination.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid.
  • a polyethylene resin containing 60 to 100% by mass, particularly 70 to 99.5% by mass of ethylene as a monomer unit is preferable.
  • ethylene as a monomer unit is preferably 60 to 100% by mass. %, Particularly 70 to 99. 5% by mass of ultra-low density polyethylene is preferred.
  • Such a polyethylene resin has excellent processability, and has a high affinity for a sealing material for a solar cell module, particularly a sealing material made of the same ethylene-based ethylene-vinyl acetate copolymer, and has very good adhesion. Excellent.
  • the thermoplastic resin layer 12A preferably contains 60% by mass or more of the olefin resin described above, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the thermoplastic resin layer 12A includes various additives such as an ultraviolet absorber, an ultraviolet stabilizer, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and an antiblocking agent as necessary, in addition to the olefin resin. You may go out.
  • the thickness of the thermoplastic resin layer 12A is not particularly limited as long as it exhibits desired adhesion to the adherend and does not impair the effects of the present invention. Specifically, the thickness of the thermoplastic resin layer 12A is preferably 1 to 200 ⁇ m, more preferably 10 to 180 ⁇ m, and more preferably 50 to 150 ⁇ m from the viewpoint of electrical insulation and weight reduction. Particularly preferred is 80 to 120 ⁇ m.
  • thermoplastic resin layer 12A in this embodiment is a single layer, it is advantageous in terms of material cost and manufacturing cost.
  • a fluororesin layer 13 is provided on the surface of the substrate 11 on the side where the thermoplastic resin layer 12A is not laminated (the lower surface in FIG. 2).
  • the fluororesin layer 13 in this way, the weather resistance and chemical resistance of the solar cell protective sheet 1A are improved.
  • the base material 11 consists of a resin film
  • stacked is a corona treatment, a plasma treatment, a primer. Surface treatment such as treatment is preferably performed.
  • the fluororesin layer 13 is not particularly limited as long as it contains fluorine.
  • the fluororesin layer 13 is constituted by a sheet having a fluorine-containing resin (fluorine-containing resin sheet), a coating film formed by applying a paint containing the fluorine-containing resin, or the like. Is done.
  • a coating film formed by applying a paint having a fluorine-containing resin is preferable.
  • the fluorine-containing resin sheet for example, a sheet obtained by processing a resin mainly composed of polyvinyl fluoride (PVF), ethylene chlorotrifluoroethylene (ECTFE), or ethylene tetrafluoroethylene (ETFE) is used.
  • PVF polyvinyl fluoride
  • ECTFE ethylene chlorotrifluoroethylene
  • ETFE ethylene tetrafluoroethylene
  • the fluororesin layer 13 is a fluorine-containing resin sheet
  • the fluororesin layer 13 is laminated on the substrate 11 via an adhesive layer.
  • the adhesive layer is composed of an adhesive having adhesiveness to the substrate 11 and the fluorine-containing resin sheet.
  • adhesives include acrylic adhesives, polyurethane adhesives, epoxy adhesives, polyester adhesives, and polyester polyurethane adhesives. These adhesives may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the fluororesin layer 13 is a coating film formed by applying a paint having a fluorine-containing resin
  • the paint containing the fluorine-containing resin is usually applied directly to the substrate 11 without using an adhesive layer.
  • the fluororesin layer 13 is laminated on the base material 11.
  • the coating material containing the fluorine-containing resin is not particularly limited as long as it is dissolved in a solvent or dispersed in water and can be applied.
  • the fluorine-containing resin contained in the paint is not particularly limited as long as it does not impair the effects of the present invention and contains fluorine. However, it is usually soluble in a paint solvent (organic solvent or water) and can be crosslinked. Things are used.
  • a fluoroolefin resin having a crosslinkable functional group examples include a hydroxyl group, a carboxyl group, an amino group, and a glycidyl group.
  • fluoroolefin resin having a crosslinkable functional group examples include “LUMIFLON” (product name) manufactured by Asahi Glass Co., Ltd., “CEFRAL COAT” (product name) manufactured by Central Glass Co., Ltd., and “FLUONATE” (product manufactured by DIC Corporation). Name) and other polymers based on chlorotrifluoroethylene (CTFE) as a main component, and polymers based on tetrafluoroethylene (TFE) such as “ZEFFLE” (trade name) manufactured by Daikin Industries, Ltd. .
  • CTFE chlorotrifluoroethylene
  • TFE tetrafluoroethylene
  • a polymer containing CTFE as a main component and a polymer containing TFE as a main component are preferable, and “LUMIFLON” and “ZEFFLE” are particularly preferable.
  • the coating material may contain a crosslinking agent, a crosslinking catalyst, a solvent and the like in addition to the fluorine-containing resin described above, and may further contain an inorganic compound such as a pigment and a filler, if necessary.
  • the coating film of fluorine-containing resin is preferably cross-linked with a cross-linking agent in order to improve weather resistance and scratch resistance.
  • the crosslinking agent is not particularly limited as long as the effects of the present invention are not impaired, and metal chelates, silanes, isocyanates, or melamines are preferably used. Assuming that the solar cell protective sheet 1A is used outdoors for a long period of time, aliphatic isocyanates are preferable as the crosslinking agent from the viewpoint of weather resistance.
  • the thickness of the fluororesin layer 13 is set in consideration of weather resistance, chemical resistance, weight reduction, etc., and is preferably 5 to 50 ⁇ m, particularly preferably 10 to 30 ⁇ m.
  • the fluororesin layer 13 may be made of a thermoplastic material, and in that case, the fluororesin layer 13 can be formed by an extrusion coating method instead of applying a paint.
  • a fluororesin layer 13 may be directly extrusion-coated on the base material 11, or another layer capable of increasing the adhesive force with the base material 11 may be interposed between the fluororesin layer 13 and the base material 11.
  • a second thermoplastic resin layer 12 ⁇ / b> C may be interposed between the fluororesin layer 13 and the substrate 11.
  • fluororesin layer 13 made of a thermoplastic material examples include an ethylene-tetrafluoroethylene copolymer (ETFE), an ethylene-chlorotrifluoroethylene copolymer, and an ethylene-tetrafluoroethylene-hexafluoropropylene copolymer.
  • ETFE ethylene-tetrafluoroethylene copolymer
  • the fluororesin layer 13 made of a thermoplastic material has an advantage of having high weather resistance.
  • ETFE is particularly preferable from the viewpoint of adhesion to the base material 11 or the second thermoplastic resin layer 12C.
  • low density polyethylene LDPE, density: 910 kg / m 3 or more, less than 930 kg / m 3
  • medium density polyethylene MDPE, density: 930 kg / m 3 or more, 942 kg / m 3 Less
  • polyethylene such as high-density polyethylene (HDPE, density: 942 kg / m 3 or more), polypropylene (PP), olefin elastomer (TPO), cycloolefin resin, ethylene-vinyl acetate copolymer (EVA), ethylene -Vinyl acetate-maleic anhydride copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, And ethylene- (meth) acrylic acid glycidyl copolymer.
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • These resin can be used individually by 1 type or in mixture of 2 or more types.
  • ethylene-vinyl acetate-maleic anhydride copolymer and ethylene-glycidyl methacrylate copolymer (EGMA) are particularly preferable. Since such a resin has a functional group and a polarity, it has a high adhesive force to the substrate 11, particularly the substrate 11 made of a resin film, and further to the substrate 11 made of a PET film.
  • EGMA is particularly preferable because it has good adhesion to both the fluororesin layer 13 made of a fluororesin containing a functional group and the substrate 11 made of PET or the like.
  • the thickness of the second thermoplastic resin layer 12C is not particularly limited as long as it exhibits desired adhesion to the substrate 11 and does not impair the effects of the present invention. Specifically, the thickness of the second thermoplastic resin layer 12C is preferably 2 to 100 ⁇ m, particularly preferably 5 to 75 ⁇ m, and further preferably 10 to 50 ⁇ m.
  • the base material 11 consists of a resin film
  • the surface of the base material 11 on the side where the thermoplastic resin layer 12A is not laminated is interposed between the base material 11 and the fluororesin layer 13.
  • the vapor deposition layer 14 may be provided, or, as shown in FIG. 5, the metal sheet 16 may be laminated via the adhesive layer 15, and the surface of the vapor deposition layer 14 or the metal sheet 16 (see FIGS. 4 and 5). 5 may be provided with the fluororesin layer 13 described above.
  • the vapor deposition layer 14 or the metal sheet 16 the moisture-proof property and weather resistance of the solar cell protective sheet 1A can be improved.
  • stacked corona treatment a plasma treatment, a primer Surface treatment such as treatment is preferably performed.
  • the vapor deposition layer 14 is comprised from inorganic materials, such as a metal or a semimetal, or an oxide, nitride, silicide, etc. of a metal or a semimetal, By being comprised from such material, the base material 11 (protective sheet for solar cells) 1A) can be provided with moisture resistance (water vapor barrier property) and weather resistance.
  • inorganic materials such as a metal or a semimetal, or an oxide, nitride, silicide, etc. of a metal or a semimetal
  • Examples of the vapor deposition method for forming the vapor deposition layer 14 include chemical vapor deposition such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition, or vacuum vapor deposition, sputtering, and ion plating.
  • a physical vapor phase method such as a method is used.
  • the sputtering method is preferable in consideration of operability and controllability of the layer thickness.
  • Examples of the metal used as the raw material of the vapor deposition layer 14 include aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium rim (Na), titanium (Ti), and lead. (Pb), zirconium (Zr), yttrium (Y) and the like.
  • Examples of the semimetal include silicon (Si) and boron (B).
  • Examples of these metal or metalloid oxides, nitrides, and oxynitrides include aluminum oxide, tin oxide, silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxynitride.
  • the vapor deposition layer 14 may be made of one kind of inorganic material or may be made of a plurality of kinds of inorganic materials.
  • the vapor deposition layer 14 may be a vapor deposition layer having a laminated structure in which the layers made of the respective inorganic materials are sequentially vapor deposited, or may be a vapor deposition layer in which a plurality of types of inorganic materials are vapor deposited simultaneously. May be.
  • the thickness of the vapor deposition layer 14 is appropriately set in consideration of the water vapor barrier property, and is changed depending on the type of inorganic material used, vapor deposition density, and the like. Usually, the thickness of the vapor deposition layer 14 is preferably 5 to 200 nm, and particularly preferably 10 to 100 nm.
  • the metal sheet 16 can also impart moisture resistance (water vapor barrier property) and weather resistance to the base material 11 (protective sheet for solar cell 1A), similarly to the vapor deposition layer 14.
  • the material of the metal sheet 16 is not particularly limited as long as it has such a function, and examples thereof include metals such as aluminum and aluminum alloys such as aluminum-iron alloys.
  • the thickness of the metal sheet 16 is not particularly limited as long as the effects of the present invention are not impaired, but from the viewpoint of low pinhole occurrence frequency, high mechanical strength, high water vapor barrier properties, and weight reduction, etc. 5 to 100 ⁇ m is preferable, and 10 to 50 ⁇ m is particularly preferable.
  • the adhesive layer 15 is composed of an adhesive having adhesiveness to the base material 11 and the metal sheet 16.
  • an acrylic adhesive, a polyurethane adhesive, an epoxy adhesive, a polyester adhesive, a polyester polyurethane adhesive, or the like is used as the adhesive constituting the adhesive layer 15. These adhesives may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the thickness of the adhesive layer 15 is not particularly limited as long as the effects of the present invention are not impaired, but it is usually preferably 1 to 20 ⁇ m and particularly preferably 3 to 10 ⁇ m.
  • thermoplastic resin layer 12A in which the thermoplastic resin layer 12A is laminated on one surface of the substrate 11 is exemplified, but the solar cell protective sheet of the present invention is not limited thereto.
  • the thermoplastic resin layer may also be laminated on the other surface of the substrate 11 (the surface opposite to the one surface).
  • the solar cell protective sheet 1 ⁇ / b> B according to the second embodiment is similar to the solar cell protective sheet 1 ⁇ / b> A according to the first embodiment.
  • the thermoplastic resin layer 12B is laminated on the surface (the upper surface in FIG. 6).
  • the thermoplastic resin layer 12B is formed on the first layer 121 and the first layer 121 laminated on the substrate 11.
  • the second layer 122 and the second layer 122 are laminated.
  • the second layer 122 is made of the same material as the thermoplastic resin layer 12A of the solar cell protective sheet 1A according to the first embodiment. Therefore, the second layer 122 is mainly composed of a thermoplastic resin, preferably the olefin resin described above, and contains the pigment described above.
  • the pigment is preferably contained in the second layer 122 in an amount of 2.5 to 35% by mass, particularly preferably 2.5 to 32.5% by mass, and more preferably 3.0 to 30% by mass. It is preferable that In particular, when titanium oxide is used as the pigment, the titanium oxide is preferably contained in the second layer 122 in an amount of 3.0 to 30% by mass, particularly preferably 5.0 to 25% by mass, and more preferably 7%. It is preferably contained in an amount of 5 to 20% by mass. When carbon black is used as the pigment, the carbon black is preferably contained in the second layer 122 in an amount of 2.5 to 30% by mass, particularly preferably 2.75 to 25% by mass, It is preferably contained in an amount of 3.0 to 20% by mass.
  • the thickness of the second layer 122 is preferably 10 to 200 ⁇ m, particularly preferably 15 to 150 ⁇ m, and further preferably 25 to 125 ⁇ m.
  • the first layer 121 is made of a material that exhibits adhesion to the base material 11. Since the first layer 121 is made of a material exhibiting adhesiveness to the base material 11, the solar cell protective sheet 1B according to the present embodiment has excellent adhesiveness between the base material 11 and the thermoplastic resin layer 12B. It becomes. On the other hand, the second layer 122 has high adhesion to the sealing material of the solar cell module due to the excellent heat-sealing action of the thermoplastic resin, particularly the olefin resin described above. Because of these high adhesive strengths, the solar cell protective sheet 1B according to the present embodiment is difficult to delaminate, and thus the inside of the solar cell module can be protected over a long period of time.
  • the first layer 121 may be a copolymer of ethylene and at least one selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester and vinyl acetate (hereinafter referred to as “copolymer F”). .) Is the main component.
  • the first layer 121 made of the above material has a high adhesive force to the base material 11, particularly the base material 11 made of a resin film, and further to the base material 11 made of a PET film.
  • the copolymer F has a high adhesive force to the base material 11, particularly the base material 11 made of a resin film, and further to the base material 11 made of a PET film.
  • the copolymer F is amorphous (non-crystalline) at room temperature and has elasticity. Therefore, even if the second layer 122 shrinks when cooled from the heated and melted state (although shrinkage is suppressed by the inclusion of the pigment), the first layer 121 is mainly composed of the copolymer F, The first layer 121 can relieve the contraction stress. Thereby, even when the first layer 121 and the second layer 122 are formed on the base material 11 by coextrusion coating, the stress acting toward the base material 11 is not easily generated. Therefore, the curl amount of the protective sheet 1B for solar cells is It will be smaller.
  • the first layer 121 is preferably composed mainly of a copolymer of ethylene and (meth) acrylic acid, a copolymer of ethylene and (meth) acrylic acid ester, or a copolymer of ethylene and vinyl acetate. These copolymers can be used alone or in combination of two or more.
  • the (meth) acrylic acid ester is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic.
  • examples thereof include propyl acid, butyl (meth) acrylate, 2-ethylhexyl acrylate, etc.
  • methyl acrylate and butyl acrylate are preferable. These can be used alone or in combination of two or more.
  • the first layer 121 is preferably composed mainly of an ethylene-methacrylic acid copolymer, an ethylene-butyl acrylate copolymer, an ethylene-methyl acrylate copolymer or an ethylene-vinyl acetate copolymer, One of these copolymers can be used alone or in combination of two or more.
  • the total content of (meth) acrylic acid, (meth) acrylic acid ester and vinyl acetate as monomer units in the copolymer F is preferably 2 to 40% by mass, and 3 to 35% by mass. It is particularly preferred that That is, in the copolymer of ethylene and (meth) acrylic acid, the content of (meth) acrylic acid, in the copolymer of ethylene and (meth) acrylic acid ester, the content of (meth) acrylic acid ester, ethylene and In the copolymer with vinyl acetate, the vinyl acetate content is preferably 2 to 40% by mass, particularly preferably 3 to 35% by mass.
  • the first layer 121 preferably contains the copolymer F as a main component. Specifically, the first layer 121 preferably contains 60% by mass or more, particularly 80% by mass or more. Preferably, it is more preferably 90% by mass or more. Naturally, the first layer 121 may be made of only the copolymer F.
  • the first layer 121 may contain various additives such as an ultraviolet absorber, an ultraviolet stabilizer, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and an antiblocking agent in addition to the resin as the main component. May be included. However, if the first layer 121 contains a pigment, the adhesiveness is lowered, and the adhesion to the substrate 11 may be lowered. Therefore, the first layer 121 preferably does not contain a pigment.
  • the thickness of the first layer 121 is preferably 5 to 150 ⁇ m, particularly preferably 10 to 100 ⁇ m, and further preferably 15 to 75 ⁇ m.
  • the ratio of the thickness of the first layer 121 to the thickness of the second layer 122 is preferably 1: 9 to 7: 3, and is 1.5: 8.5 to 6.5: 3.5. Particularly preferred is 2: 8 to 6: 4.
  • the solar cell protective sheet 1B according to the present embodiment has a smaller curl amount.
  • the melt flow rate (MFR) of the constituent resin (copolymer F) of the first layer 121 and the olefin resin of the second layer 122 is preferably 1 to 20 g / 10 min, and particularly 2 to 10 g / 10 min. It is preferable. When the MFR of both resins is within the above range, the first layer 121 and the second layer 122 can be formed by coextrusion coating.
  • thermoplastic resin layer 12B in this embodiment consists of the 1st layer 121 and the 2nd layer 122
  • this invention is not limited to this, Unless the effect of this invention is impaired, Other layers may be provided.
  • a third layer may be provided between the first layer 121 and the second layer 122.
  • the solar cell protective sheet 1B according to the present embodiment is similar to the solar cell protective sheet 1A according to the first embodiment, for example, other layers, for example, a fluororesin layer 13 and a second thermoplastic resin layer 12C. Further, a vapor deposition layer 14, an adhesive layer 15, a metal sheet 16 and the like may be provided.
  • thermoplastic resin composition constituting the thermoplastic resin layer 12A is It is preferable to form the thermoplastic resin layer 12 ⁇ / b> A on the substrate 11 by extrusion coating on at least one surface of the substrate 11.
  • thermoplastic resin layer 12A is melted and kneaded, and the substrate 11 is moved at a constant speed.
  • the molten resin composition is extruded and laminated on one surface of the base material 11 to form a thermoplastic resin layer 12A on the base material 11 to obtain a solar cell protective sheet 1A.
  • the first layer 121 of the thermoplastic resin layer 12B is configured.
  • the first resin composition and the second resin composition constituting the second layer 122 are placed on at least one surface of the base material 11 so that the first resin composition is on the base material 11 side. It is preferable to form the thermoplastic resin layer 12 ⁇ / b> B including the first layer 121 laminated on the substrate 11 and the second layer 121 laminated on the first layer 121 by extrusion coating.
  • the first resin composition and the second resin composition are respectively melted and kneaded, and the substrate 11 is moved at a constant speed.
  • the melted first resin composition and second resin composition are coextruded and laminated on one surface of the base material 11, and the first layer 121 and the second layer 122 are formed on the base material 11.
  • the thermoplastic resin layer 12B is formed to obtain the solar cell protective sheet 1B.
  • the solar cell protective sheet 1 can be manufactured with high productivity and at low cost. Moreover, since it is not necessary to separately provide an adhesive layer for adhering the solar cell protective sheets 1A and 1B to the sealing material of the solar cell module, it is possible to prevent deterioration over time due to decomposition of the adhesive or the like. it can.
  • thermoplastic resin layer is formed on the surface of the base material 11 where the other layer is not formed.
  • 12A and 12B may be formed.
  • the temperature at which the resin composition forming the thermoplastic resin layers 12A and 12B is melted is such that the substrate 11 is not deformed by the temperature (heat) of the melted resin composition, and is preferably 80 to 350 ° C., 150 A temperature of ⁇ 300 ° C. is particularly preferred.
  • the discharge amount of the resin composition for forming the thermoplastic resin layers 12A and 12B from the T-die film forming machine is appropriately determined according to the thickness of the target thermoplastic resin layers 12A and 12B and the moving speed of the base material 11. Adjusted.
  • the base material 11 is moved (conveyed) in the longitudinal direction at a constant speed by, for example, a roll-to-roll system, and the moving speed is made of a T-die of a resin composition that forms the thermoplastic resin layers 12A and 12B. It adjusts suitably according to the discharge amount from a film machine.
  • the base material 11 can be formed by only (co) extrusion coating and laminating the resin composition melted from the T-die film forming machine on one surface of the base material 11.
  • the thermoplastic resin layers 12A and 12B can be firmly bonded to each other, and the solar cell protective sheets 1A and 1B can be manufactured with high productivity.
  • FIG. 7 is a schematic cross-sectional view of a solar cell module according to an embodiment of the present invention.
  • the solar cell module 10 according to the present embodiment includes a plurality of solar cells 2 made of crystalline silicon, amorphous silicon, or the like, which are photoelectric conversion elements, and a sealing material made of an electrical insulator that seals the solar cells 2 ( Packing layer) 3, a glass plate 4 laminated on the surface (upper surface in FIG. 7) of the sealing material 3, and a back surface protection sheet (laminated on the lower surface in FIG. 7) It is comprised from the protection sheet 1 for solar cells (protection sheet 1A, 1B for solar cells in the said embodiment) as a back sheet
  • the solar cell protective sheet 1 is laminated on the encapsulant 3 so that the second layer 122 of the thermoplastic resin layer 12A or the thermoplastic resin layer 12B is in contact with the encapsulant 3, and is a thermoplastic resin, preferably Adhesive strength to the sealing material 3 is high due to the above-described layers mainly composed of the olefin resin.
  • the solar cell protective sheet 1B is used as the solar cell protective sheet 1, the adhesion between the substrate 11 and the thermoplastic resin layer 12B is also excellent. Because of these high adhesive forces, the inside of the solar cell module 10 according to the present embodiment is protected by the solar cell protective sheet 1 for a long period of time.
  • the solar cell protective sheet 1 in the present embodiment has a small amount of curl, warping of the obtained solar cell module 10 is suppressed. Therefore, it is possible to prevent problems caused when the solar cell module 10 is installed or damage of the solar cell module 10 due to warpage of the solar cell module 10.
  • the material of the sealing material 3 is preferably an olefin resin, and is preferably an olefin resin exemplified as a main component of the second layer 122 of the thermoplastic resin layer 12A or the thermoplastic resin layer 12B,
  • an ethylene-vinyl acetate copolymer (EVA) is preferable from the viewpoints of high gas barrier properties against oxygen and the like, easy crosslinking, and availability.
  • EVA ethylene-vinyl acetate copolymer
  • the affinity with the second layer 122 of the thermoplastic resin layer 12A or the thermoplastic resin layer 12B mainly composed of the olefin resin is increased, and the thermoplastic resin layer The adhesive force between 12A and 12B and the sealing material 3 becomes higher.
  • the method for producing the solar cell module 10 is not particularly limited.
  • the solar cell 2 is sandwiched between two sheets constituting the encapsulant 3, and the solar cell protective sheet is provided on one exposed surface of the sheet. 1.
  • the solar cell module 10 can be manufactured by installing the glass plate 4 on the other exposed surface and pressing and integrating them while heating. At this time, the protection sheet 1 for solar cells is joined to the sealing material 3 by thermal fusion between the thermoplastic resin layers 12 ⁇ / b> A and 12 ⁇ / b> B and the sealing material 3.
  • a flexible solar cell module can be obtained by using a flexible substrate for the solar cell.
  • the flexible solar cell module can be fitted to an object having an arched or parabolic wall surface, it can be installed on a dome-shaped building or a soundproof wall of a highway. .
  • Example 1 One side of a PET film (trade name: Melinex S, thickness 125 ⁇ m, manufactured by Teijin DuPont Films Ltd.) as a substrate was subjected to corona treatment (output 2000 W). Then, using a T-die film forming machine, 97.5 parts by mass of polyethylene resin (manufactured by Tosoh Corporation, trade name: Lumitac 43-1, density: 905 kg / m 3 , heat of fusion ⁇ H: 79 J / g) and oxidation as a pigment A mixture of 2.5 parts by weight of titanium (manufactured by Ishihara Sangyo Co., Ltd., trade name: Typeke CR-60, average particle size: 0.21 ⁇ m) was melted at a temperature of 300 ° C., and the thickness of the PET film was adjusted to 150 ⁇ m. The corona-treated surface was extrusion coated to form a thermoplastic resin layer, and a solar cell protective sheet having the configuration shown in FIG.
  • the density of the polyethylene resin was measured according to JIS K7112: 1999.
  • the heat of fusion ⁇ H of the polyethylene resin was measured as follows.
  • Example 2 A protective sheet for a solar cell was produced in the same manner as in Example 1 except that the blending amount of the polyethylene resin was 85.0 parts by mass and the blending amount of titanium oxide was 15.0 parts by mass.
  • Example 3 A protective sheet for a solar cell was produced in the same manner as in Example 1 except that the blending amount of the polyethylene resin was 65.0 parts by mass and the blending amount of titanium oxide was 35.0 parts by mass.
  • Example 4 A protective sheet for a solar cell was produced in the same manner as in Example 2 except that the titanium oxide was changed to magnesium oxide (manufactured by Tateho Chemical Co., Ltd., trade name: # 500, average particle size: 5 ⁇ m).
  • Example 5 A protective sheet for a solar cell was produced in the same manner as in Example 2, except that the titanium oxide was changed to cerium oxide (trade name: Nano Tek CeO 2 , average particle diameter: 0.012 ⁇ m, manufactured by CI Kasei Co., Ltd.).
  • Example 6 A protective sheet for a solar cell was produced in the same manner as in Example 2 except that titanium oxide was changed to talc (trade name: MICRO ACE P-3, average particle diameter: 5.0 ⁇ m, manufactured by Nippon Talc Co., Ltd.).
  • Example 7 A protective sheet for a solar cell was produced in the same manner as in Example 2 except that the titanium oxide was changed to calcium carbonate (manufactured by Nitto Flour Chemical Co., Ltd., trade name: NN # 500, average particle size: 4.4 ⁇ m).
  • Example 8 Titanium oxide was changed to carbon black (trade name: # 45L, average particle size: 0.024 ⁇ m, manufactured by Mitsubishi Chemical Corporation), the blending amount of polyethylene resin was 97.0 parts by mass, and the blending amount of carbon black was 3.
  • a protective sheet for solar cell was produced in the same manner as in Example 1 except that the content was 0 parts by mass.
  • Example 9 One side of a PET film (trade name: Melinex S, thickness 125 ⁇ m, manufactured by Teijin DuPont Films Ltd.) as a substrate was subjected to corona treatment (output 2000 W). Then, using a T-die film forming machine, an ethylene-butyl acrylate copolymer (manufactured by Arkema, trade name: LOTRYL 30BA02, butyl acrylate content: 30 mass%, hereinafter referred to as “copolymer A”), 85.0 parts by mass of polyethylene resin (trade name: Lumitac 43-1, density 905 kg / m 3 ) manufactured by Tosoh Corporation, and titanium oxide as a pigment (trade name: Typeke CR-60, average particle diameter as a pigment) : 0.21 ⁇ m) 15.0 parts by mass of the mixture were melted at a temperature of 300 ° C., respectively, so that the thicknesses became 40 ⁇ m and 110 ⁇ m, and the copolymer
  • the first layer (copolymer a: thickness 40 [mu] m) and a second layer (polyethylene having a density of 905 kg / m 3 Resin: forming a thermoplastic resin layer having a thickness of 110 [mu] m), to obtain a protective sheet for a solar cell of the configuration shown in FIG.
  • Example 10 Titanium oxide in the second layer was changed to carbon black (Mitsubishi Chemical Co., Ltd., trade name: # 45L, average particle size: 0.024 ⁇ m), the blending amount of polyethylene resin was 97.0 parts by mass, and the blending of carbon black A protective sheet for solar cell was produced in the same manner as in Example 9 except that the amount was 3.0 parts by mass.
  • carbon black Mitsubishi Chemical Co., Ltd., trade name: # 45L, average particle size: 0.024 ⁇ m
  • Example 1 A protective sheet for a solar cell was produced in the same manner as in Example 1 except that titanium oxide was not blended and the blending amount of the polyethylene resin was 100.0 parts by mass.
  • the solar cell protective sheet of the example had a small curl amount.
  • the protective sheet for solar cell according to the present invention is suitably used as a back sheet for a solar cell module, for example.

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PCT/JP2012/056669 2011-03-30 2012-03-15 太陽電池用保護シートおよびその製造方法、ならびに太陽電池モジュール WO2012132921A1 (ja)

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JP2012209461A (ja) 2012-10-25
US20140069495A1 (en) 2014-03-13
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